JPS6289733A - Molded article of nonfibrous high polymer having electric conductivity and production thereof - Google Patents

Abstract

PURPOSE:To obtain a molded article of a nonfibrous high polymer having electric conductivity, by adsorbing monovalent copper ions on a molded article of a nonfibrous high polymer containing cyano groups and bringing the resultant molded article into contact with a sulfur compound. CONSTITUTION:Monovalent copper ions are adsorbed on a molded article of a nonfibrous high polymer containing cyano groups (e.g. a molded article in the form of film, block, etc.), and the copper ions are converted into copper sulfide by a method for bringing the molded article into contact with an aqueous bath containing a sulfur compound in a dissolved state or sulfur dioxide or hydrogen sulfide in a gaseous state, etc., to afford the aimed molded article of the nonfibrous high polymer having electric conductivity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a non-fibrous polymer molded article having electrical conductivity.

Conventionally, a method for manufacturing acrylic fibers having conductivity has already been known (Japanese Patent Application Laid-open No. 51873/1983). This method involves adsorbing monovalent copper ions onto acrylic fibers and then applying a reducing agent to reduce and precipitate metallic copper within the fibers. The method for producing a non-fibrous polymer molded article is not disclosed.

The present inventors have completed the present invention as a result of various studies on the production of non-fibrous polymer molded products such as conductive films and sheets.

That is, according to the present invention, monovalent copper ions are adsorbed onto a non-fibrous polymer molded article containing a cyano group, and then monovalent copper ions are absorbed into the molded article to which monovalent copper ions are adsorbed. Provided is a method for producing a non-fibrous polymeric molded article having electrical conductivity, which comprises contacting the present invention with a sulfur compound exhibiting copper sulfide forming reactivity and converting the copper ions into copper sulfide.

The present inventors have conducted various studies on the above-mentioned known methods. Then, in the known method, 1
The technical concept of producing conductive fibers by reducing and precipitating valence copper ions as metallic copper on fibers using a reducing agent is incorrect, and the conductive fibers obtained in the examples in the publication are not strictly As a result of analysis, it was found that the substance responsible for the conductivity was not metallic copper but copper sulfide, and in order to obtain a conductive product, the monovalent copper ion was
It has been found that it is necessary to react a sulfur compound exhibiting copper sulfide-forming reactivity to convert monovalent copper ions to copper sulfide.

The present invention was made based on this knowledge, and, unlike the above-mentioned known techniques, is an attempt to produce a non-fibrous polymer molded product having conformability.

The raw material to be processed used in the present invention is a non-fibrous polymer molded product containing a cyano group (hereinafter also simply referred to as a molded product), and is molded into a film (or sheet), block, rod, or plate shape. It is a thing. Since cyano groups and monovalent copper ions have a strong affinity, it is possible to use methods such as graft polymerization not only for polymer molded products that have cyano groups in their molecular structure, but also for already molded polymer molded products. By introducing a cyano group, the product of the present invention can be produced. That is, even in the case of a polymer substance having no cyano group, a molded article into which a cyano group is introduced at any stage can be used as the raw material molded article to be treated of the present invention.

In the present invention, monovalent copper ions are first adsorbed onto this molded article. This monovalent copper ion adsorption treatment can be carried out by bringing the molded product into contact with an aqueous bath containing monovalent copper ions. As the monovalent copper ion source used in this case, a monovalent copper salt itself may be used, or a combination of a divalent copper salt and a reducing agent may be used.

In this combination of a divalent copper salt and a reducing agent, divalent copper ions are reduced to monovalent copper ions by the action of the reducing agent. In this case, as the divalent copper salt, for example, cupric sulfate, cupric chloride, cupric nitrate, etc. are used, and as the reducing agent, it is possible to reduce divalent copper ions to monovalent copper ions. For example, metal copper, hydroxylamine, ferrous sulfate, ammonium vanadate, furfural, sodium hypophosphite, or glucose can be used, and in addition, sulfur compounds as described below can be used. can also be used because it has reducing properties. Moreover, as the monovalent copper salt, cuprous chloride, its ammonium complex salt, etc. are used.

In addition, in the present invention, in order to adjust the pH of the aqueous bath containing monovalent copper ions, if necessary, the acid or salt may be
)I used as a pH regulator, and examples of such pH regulators include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid; organic acids such as citric acid and acetic acid; or salts thereof, or combinations of acids and salts; For example, a combination of citric acid and disodium phosphate can be used. By using this pl+ regulator.

The rate of adsorption of monovalent copper ions from the aqueous bath to the surface of the molded article can be adjusted.

The molded product to which monovalent copper ions are adsorbed as described above is
Next, the copper sulfide is bonded onto the molded article by reacting with a sulfur compound. The sulfur compound used in the present invention may be any compound that exhibits copper sulfide forming reactivity toward monovalent copper ions, and a sulfur compound that can release sulfur atoms or sulfur ions is used. Such sulfur compounds are conventionally known, and include, for example, sodium sulfide, sodium dithionite, sodium thiosulfate, sulfur dioxide, hydrogen sulfide, Rongalit C or 2, and the like. This copper sulfide forming reaction can be carried out using an aqueous bath containing the sulfur compound in a dissolved state, or it can be carried out using a gaseous sulfur compound. As the gaseous sulfur compound, sulfur dioxide, hydrogen sulfide, etc. can be preferably used. In addition, when carrying out the copper sulfide formation reaction using an aqueous bath containing a sulfur compound, if necessary,
In order to adjust the pH of the aqueous bath, acids or salts are used as pH adjusting agents, and as such pH adjusting agents, those indicated above can be used. By using this pH adjuster, the binding rate (reaction rate) of copper sulfide from the aqueous bath to the surface of the molded article can be adjusted.

In the present invention, the treatment temperature for adsorbing monovalent copper ions and converting the monovalent copper ions into copper sulfide is such that the reaction proceeds quickly at high temperatures, but if the temperature is high, the molded product will deform. In some cases, the reaction takes time at low temperatures, so there is an appropriate temperature range. That is, approximately 30°C to 120°C
C. is a suitable temperature range, but it is more economical to carry out both the adsorption of monovalent copper ions and the conversion to copper sulfide at a temperature of 60.degree. C. or higher, as this can save time and is more economical.

A conductive molded product can be obtained as described above.

When this material was analyzed using X-rays, it was found that digenite (Cu
sps) Chalcosite (CuJ) Covellite (CuS)
It was possible to observe the diffraction lines of , and it became clear that copper sulfide was contained.

The interplanar spacing (person) of the diffraction lines is as follows.

Table-1 EXAMPLES The present invention will be described in detail below with reference to Examples.

Example 1 About 2 g of acrylic fiber (Bonnell 2 denier, 51 aun, cut type 17B manufactured by Mitsubishi Rayon) was mixed with about 10 g of dimethylformamide (hereinafter referred to as DMF and 1I18).
After heating the solution to 0 mΩ and leaving it for a while to degas it, about 30 cc of the solution was transferred to a petri dish, and heated from below while simultaneously blowing hot air to vaporize and remove DNF.

The obtained film is mainly composed of acrylonitrile, has a diameter of 7.5 aa, a thickness of 0.13 m +++, and a weight of about 0.5 aa.
It was 65 g. This film was treated in a 200 mQ solution containing 2 parts cupric sulfate and 10% hydroxylamine hydrochloride based on the weight of the film at 80° C. for 2 hours by gradually increasing the temperature from low temperature. After thorough washing with water, the temperature was gradually raised from low temperature in a 200 m Q bath containing 8 g of sodium dithionite, 30 g of disodium phosphate, and 8 g of sodium citrate per liter of water, and treated at 70°C for 1 hour. did. The surface resistivity of the obtained film (ρS
) was 160Ω. The X-rays of the sulfide steel bonded to the film surface were mainly composed of digenite, with covellite diffraction lines observed.

Example 2 A film mainly composed of acrylonitrile produced in the same manner as in Example 1 was treated in 200 m Q of a solution containing 10% cuprous chloride based on its weight at 90°C for 2 hours.
After thorough water washing, it was treated for 10 hours at 45° C. in a Loom Q aqueous bath containing 8 g of sodium thiosulfate, 10 g of hydroxylamine hydrochloride, 20 g of disodium phosphate, and 8 g of citric acid per liter.

The surface resistivity (ρS) of the obtained film was 220Ω.

Example 3 5 g of nylon film (80115 manufactured by Toshi) was added to 200 m Q of an aqueous solution containing Log ammonium persulfate and Log sodium acid sulfite per liter at room temperature for 30 g.
After immersing the film for a minute and pulling it out, the water droplets on both sides of the film were wiped off with paper and placed in a stainless steel container.The container was depressurized with mercury to 15 mm using a vacuum pump, and then acrylonitrile vapor was introduced.

The graft polymerization reaction was carried out at 38 to 40°C for 3 hours. The resulting film increased in thickness by 33% and weight by 32.8% due to graft polymerization. When this material was treated in the same manner as in Example 1, the conductive film obtained was a completely brown transparent film with a surface resistivity (ρS) of about 200Ω.

Example 4 Approximately 1 g of a film containing acrylonitrile as a main component produced by the method shown in Example 1 was
% of cupric sulfate and 10% of hydroxylamine hydrochloride, the temperature was gradually raised from low temperature to 8.
It was treated at 0°C for 2 hours. Next, after washing it thoroughly with water,
The container was placed in a closed container having a gas inlet, and sulfur dioxide gas was injected until the pressure inside the container reached 0.5 kg/aI in terms of gauge pressure, and treatment was carried out for 90 minutes while maintaining the temperature at 105 to 110'C.

After cooling, the film was taken out, thoroughly washed with water, and dried. In this way, a light brown conductive film having a surface resistivity (ρ5) of 600Ω was obtained. Also.

Similar results were obtained when hydrogen sulfide was used instead of the sulfur dioxide gas.

Example 5 A conductive film was obtained in the same manner as in Example 2, except that the sulfur compound shown below was used instead of the sodium thiosulfate used to form copper sulfide.

Table-2

Claims (3)

[Claims] (1) After adsorbing monovalent copper ions to a non-fibrous polymeric molded article containing cyano groups, the molded article to which the monovalent copper ions have been adsorbed has copper sulfide formation reactivity toward the monovalent copper ions. 1. A method for producing a non-fibrous polymer molded article having electrical conductivity, which comprises contacting a sulfur compound exhibiting the following to convert the copper ions into copper sulfide. (2) The method according to claim 1, wherein the molded article on which the monovalent copper ions have been adsorbed is brought into contact with an aqueous bath containing the sulfur compound in dissolved form. (3) The method according to claim 1, wherein the molded article on which monovalent copper ions have been adsorbed is brought into contact with sulfur dioxide or hydrogen sulfide in gaseous form.